1. Field of the Invention
The present invention relates to the detection of noxious chemical species by means of chemoselective hyperbranched polymeric compounds. More particularly, the invention relates to the detection of toxic or explosive chemical vapors, such as chemical agents or nitro-substituted species, respectively, by sorbent materials comprising chemoselective hyperbranched polymeric molecules.
2. Description of Related Art
Determining and/or monitoring the presence of certain chemical species within an environment, e.g., pollutants, toxic substances and other predetermined compounds, is becoming of increasing importance with respect to such fields as health, environmental protection, resource conservation, and chemical processes. Devices for the molecular recognition of noxious species or other analytes typically include (1) a substrate and (2) a molecular recognition coating upon the substrate. These devices may be used, for example, in chemical vapor sensing or the selective separation of gases by gas chromatography. Small molecular recognition devices are described in Grate et al., Sensors and Actuators B, 3, 85–111 (1991) and Grate et al., Analytical Chemistry, Vol. 65, No. 14, Jul. 15, 1993, both of which are incorporated herein by reference.
Frequently, the substrate is a piezoelectric material or a waveguide, which can detect small changes in mass. One illustrative example of a device relying upon molecular recognition as a surface is known as a surface acoustic wave (SAW) sensor. SAW devices function by generating mechanical surface waves on a thin slab of a piezoelectric material, such as quartz, that oscillates at a characteristic resonant frequency when placed in a feedback circuit with a radio frequency amplifier. The oscillator frequency is measurably altered by small changes in mass and/or elastic modulus at the surface of the SAW device.
SAW devices can be adapted to a variety of gas-phase analytical problems by designing or selecting specific coatings for particular applications. The use of chemoselective polymers for chemical sensor application is well established as a way to increase the sensitivity and selectivity of a chemical sensor with respect to specific classes or types of analytes. Typically, a chemoselective polymer is designed to contain functional groups that can interact preferentially with the target analyte through dipole-dipole, Van der Waal's, or hydrogen bonding forces. For example, strong hydrogen bond donating characteristics are important for the detection of species that are hydrogen bond acceptors, such as toxic organophosphorus compounds. Increasing the density of hydrogen bond acidic binding sites in the coating of a sensor results in an increase in sensitivity.
Chemoselective films or coatings used with chemical sensors have been described by McGill et al. in Chemtech, Vol. 24, No. 9, 27–37 (1994). The materials used as the chemically active, selectively absorbent layer of a molecular recognition device have often been polymers, as described in Hansani in Polymer Films in Sensor Applications (Technomic, Lancaster, Pa. 1995). For example, Ting et al. investigated polystyrene substituted with hexafluoroisopropanol (HFIP) groups for its compatibility with other polymers in Journal of Polymer Science: Polymer Letters Edition, Vol. 18, 201–209 (1980) Later, Chang et al. and Barlow et al. investigated a similar material for its use as a sorbent for organophosphorus vapors, and examined its behavior on a bulk quartz crystal monitor device in Polymer Engineering and Science, Vol. 27, No. 10, 693–702 and 703–15 (1987). Snow et al. (NRL Letter Report, 6120-884A) and Sprague et al. (Proceedings of the 1987 U.S. Army Chemical Research Development and Engineering Center Scientific Conference on Chemical Defense Research, page 1241) reported making materials containing HFIP that were based on polystyrene and poly(isoprene) polymer backbones, where the HFIP provided strong hydrogen bond acidic properties. These materials were used as coatings on molecular recognition devices, such as SAW sensors, and showed high sensitivity for organophosphorus vapors. However, both the parent polymers and the HFIP-containing materials were glassy or crystalline at room temperature. Because vapor diffusion may be retarded in glassy or crystalline materials, the sensors produced were slow to respond and recover. Further, these are polymeric materials and, like all polymers, they can vary significantly from batch to batch in precise composition, purity and yield. Additional information is reported in Polym. Eng. Sci, 27, 693 and 703–715 (1987).
Vicari et al., U.S. Pat. No. 6,114,489, issued Sep. 5, 2000, discloses reactive hyper-branched polymers containing terminal hydroxy, carboxy, epoxy, and isocyanate groups. The compounds are useful as components in powder coating compositions for the formation of hard, impact resistant films. Examples of the preferred hyperbranched polyesters are those formed from α,α-bis(hydroxymethyl)-propionic acid. The backbone of these hyperbranched polymers are composed of polyester units.
Okawa et al., U.S. Pat. No. 6,140,525 issued Oct. 31, 2000, discloses a class of hyperbranched polymers that are prepared by contacting macromonomers that have both silicon hydride and unsaturated organic terminal groups with group VIII metal catalysts. The hyperbranched polymers are useful as surfactants, gelling agents, drug delivery systems, and polymeric absorbents. The hyperbranched polymer backbones are comprised of a combination of siloxane and carbosilane segments. Examples of preferred macro-monomers include (HSi(CH3)2O)2Si(CH3)OSi(CH3)2(CH2)2(Si(CH3)2O)nSi(CH3)2CH═CH2, where n is 10 to 100.
Decker et al., U.S. Pat. No. 6,001,945, issued Dec. 14, 2001, discloses hyperbranched polymers containing silicon atoms and a method of making these materials. The exchange (condensation) reaction that forms the hyperbranched polymers results in the elimination of an alcohol by-product and the formation of hyperbranched polymer backbones comprised of siloxane linkages.
The inventors have now discovered a class of hyperbranched molecules that can be used to produce hydrogen bond acidic coatings for chemical sensor applications. Using the hyperbranched molecules that are highly functionalized results in significant sensitivity improvements. Further, the chemoselective hyper-branched molecules of the present invention exhibit, not only improved sensitivity to organophosphorus species, but also high selectivity and sensitivity toward nitro-substituted chemical vapors, and are thus also useful for detecting the presence of explosives. Conventional explosives, such as trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5-trinitro-1,3,5,7-tetrazocine (HMX), may be contained in unexploded munitions, e.g., buried below the surface of the ground. Such munitions exude or leak vapors of the explosive. These vapors are typically concentrated in the surrounding soil and then migrate to the surface where they can be detected by the compounds, devices and methods of the invention.